Amine-epoxy autocatalytic polymers and polyurethane products made therefrom

ABSTRACT

The present invention pertains to low emission polyurethane products based on autocatalytic polymers made by reaction of epoxide resins with compounds containing secondary and/or tertiary amines bearing a reactive hydrogen and to processes for their manufacture.

The present invention pertains to highly reactive autocatalytic polymersmade by reaction of epoxide resins with compounds containing primary,secondary and/or tertiary amines bearing reactive hydrogen, to processesfor their manufacture and to products produced therefrom.

Polyether polyols based on the polymerization of alkylene oxides, and/orpolyester polyols, are the major components of a polyurethane systemtogether with isocyanates. Polyols can also be filled polyols, such asSAN (Styrene/Acrylonitrile), PIPA (polyisocyanate polyaddition) or PHD(polyurea) polyols, as described in “Polyurethane Handbook”, by G.Oertel, Hanser publisher. These systems generally contain additionalcomponents such as cross-linkers, chain extenders, surfactants, cellregulators, stabilizers, antioxidants, flame retardant additives,eventually fillers, and typically catalysts such as tertiary aminesand/or organometallic salts.

The organometallic catalysts used for making polyurethanes, such as leador mercury salts, can raise environmental issues due to leaching uponaging of the polyurethane products. Others, such as tin salts, are oftendetrimental to polyurethane aging.

The commonly used tertiary amine catalysts, can also give rise toundesirable properties, particularly in flexible, semi-rigid and rigidfoam applications. Freshly prepared foams using these catalysts oftenexhibit the typical odor of the amines and give rise to increasedfogging (emission of volatile products).

The presence, or formation, of even traces of tertiary amine catalystvapors in polyurethane products having vinyl films or polycarbonatesheets exposed thereto can be disadvantageous. Specifically, thetertiary amine catalysts present in polyurethane foams have been linkedto the staining of the viny film and degradation of polycarbonatesheets. This PVC staining and polycarbonate decomposition problems areespecially prevalent in environments wherein elevated temperatures existfor long periods of time, such as in automobile interiors.

Various solutions to this problem have been proposed. One is the use ofamine catalysts which contain a hydrogen isocyanate reactive group, thatis a hydroxyl or a primary and/or a secondary amine. Such a compound isdisclosed in EP 747,407. Other types of reactive monol catalysts aredescribed in U.S. Pat. Nos. 4,122,038, 4,368,278, 4,510,269 and5,539,007. Since they are monofunctional, these reactive amines act aschain stoppers and have a detrimental effect on the polymer build up andaffect polyurethane product physical characteristics. Other types ofreactive amine catalysts are claimed in U.S. Pat. No. 3,448,065, in EP677,540 and in EP 1,109,847. A reported advantage of the catalystcompositions is that they are incorporated into the polyurethaneproduct. However those catalysts have to be used at high levels in thepolyurethane formulation to compensate for their lack of mobility duringthe reactions.

Various other means have been proposed for incorporating a reactiveamine into a polyol. Modification of conventional polyols by partialamination has been disclosed in U.S. Pat. No. 3,838,076.Pre-polymerization of reactive amine catalysts with a polyisocyanate anda polyol is reported in PCT WO 94/02525. Use of specific amine-initiatedpolyols is proposed in EP 539,819, in U.S. Pat. No. 5,672,636 and in WO01/58,976. While these approaches can reduce the amount of aminecatalyst required in the system, there are disadvantages associated witheach process.

Modifications of polyether polyols along the length of the polyol chainwith epoxy resin-diamine or epoxy resin -amino-alcohol adducts aredescribed in U.S. Pat. Nos. 4,518,720, 4,535,133 and 4,609,685. Theaddition of epoxy along the internal length of the polyol chain isreported to increase the overall functionality of the polyol chain.Flexible foam produced from such polyols reportedly have equivalentfirmness and better elongation properties than foams made with a similarmolecular weight unmodified polyol. Polyepoxides containing at least onetertiary nitrogen as described in U.S. Pat. No. 4,775,558 are reportedto improve the thermal stability of polyurethane products.

Quaternary amine based catalyst compositions using epoxide chemistry aredescribed in U.S. Pat. No. 3,010,963, in U.S. Pat. No. 4,404,120 and inU.S. Pat. No. 4,040,992. These are effective for isocyanatetrimerization, an undesirable reaction in flexible foams, since it givessofter foam and poor aging characteristics.

Therefore, there continues to be a need for development of reactivepolymers so that the addition of low molecular weight tertiary amines ascatalysts for the formation of polyisocyanate polyaddition products canbe avoided to the greatest possible extent. The polymers-should besuitable for the preparation of flexible, compact or cellularpolyisocyanate polyaddition products and should be readily miscible withother synthesis components.

It is an object of the present invention to provide a reactive polymerproduced from reaction of an epoxy resin with compounds containing anamine to form a tertiary amine or with a compound containing a tertiaryamine and at least one reactive hydrogen capable of reacting with epoxymoiety. Such polymers are useful in the production of polyurethaneproducts containing a reduced level of conventional tertiary aminecatalysts, a reduced level of reactive amine catalysts or production ofsuch products in the absence of such amine catalysts. It is an anotherobjective of the present invention to produce polyurethane productscontaining a reduced level of organometallic catalyst or to produce suchproducts in the absence of organometallic catalysts. With the reductionof the amount of amine and/or organometallic catalysts needed orelimination of such catalysts, the disadvantages associated with suchcatalysts can be minimized or avoided.

It is another object of the invention to have a process to adjustreactivity, such as gelation rate, and processing of a polyurethanesystem without having to rely on amine and/or organometallic catalysts.

It is a further object of the present invention to provide autocatalyticpolymers made from tertiary amine epoxide adducts so that the industrialmanufacturing process of the polyurethane product using theseautocatalytic polymers and the physical characteristics of thepolyurethane products made therefrom are not adversely affected and mayeven be improved by the reduction in the amount of conventional orreactive amine catalysts or in elimination of the amine catalyst, and/orby reduction or elimination of organometallic catalysts.

In a further aspect, the present invention is a process for theproduction of a polyurethane product by reaction of a mixture of

-   -   (a) at least one organic polyisocyanate with    -   (b) a polyol composition comprising

-   (b1) from 60 to 99.5 percent by weight of at least one polyol    compound having a functionality of 2 to 8 and a hydroxyl number of    from 15 to 800 and

-   (b2) from 0.5 to 40 percent by weight of at least one polymer    compound having a functionality of 2 to 12, a hydroxyl number of    from 15 to 600 and containing at least one tertiary amine group,    wherein the weight percent is based on the total amount of polyol    composition (b), and (b2) is obtained by the reactions of an epoxy    resin (b3) and an amine wherein the amine is either a primary or a    secondary amine or a molecule containing at least one tertiary    nitrogen and at least one reactive hydrogen able to react with the    epoxide; or (b2) is (b4) a hydroxyl-tipped prepolymer obtained from    the reaction of an excess of (b2) or a mixture thereof with a    polyisocyanate; or (b2) is (b5) a blend of several epoxides (b3)    modified with one or more types of amines containing each at least    one reactive hydrogen;    -   (c) optionally in the presence of a blowing agent; and    -   (d) optionally additives or auxiliary agents known per se for        the production of polyurethane foams, elastomers and/or        coatings.

In another embodiment, the present invention is a process whereby part,or the whole, of polyol (b1) is a tertiary amine based polyol andexhibits autocatalytic characteristics.

In another embodiment, the present invention is a process wherebyautocatalytic polyol (b1) and/or autocatalytic polymer (b2) havespecific blowing and/or gelling characteristics and polymer (b2) is ableto replace at least 10 percent of the conventional catalysts, morepreferably 30 percent and most preferably at least 50 percent of aconventional amine catalyst.

In another embodiment, the present invention is a process as disclosedabove wherein the polyisocyanate (a) contains at least onepolyisocyanate that is a reaction product of a excess of polyisocyanatewith a polymer as defined by (b2).

In a further embodiment, the present invention is a process as disclosedabove where the polyol (b) contains a polyol-terminated prepolymerobtained by the reaction of an excess of polyol with a polyisocyanatewherein the polyol is a polymer as defined by (b2).

The invention further provides for polyurethane products produced by anyof the above processes.

In still another embodiment, the present invention is anisocyanate-terminated prepolymer based on the reaction of a polymer asdefined by (b2) with an excess of a polyisocyanate.

In yet another embodiment, the present invention is a polyol-terminatedprepolymer based on the reaction of a polyisocyanate with an excess ofpolymer as defined by (b2).

The polymers containing bonded tertiary amine functions as disclosed inthe present invention are catalytically active and accelerate theaddition reaction of organic polyisocyanates with polyhydroxyl orpolyamino compounds and the reaction between the isocyanate and theblowing agent such as water or a carboxylic acid or its salts. Theaddition of these polymers to a polyurethane reaction mixture reduces oreliminates the need to include a conventional tertiary amine catalyst oran organometallic catalyst within the mixture. Since these polymers (b2)contain reactive hydrogens, they can react with the isocyanate andbecome part of the polymer. Their addition to polyurethane reactionmixtures can also reduce the mold dwell time in the production of moldedfoams or improve some polyurethane product properties.

In accordance with the present invention, a process for the productionof polyurethane products is provided, whereby polyurethane products ofrelatively low odor and low emission of amine catalyst are produced.Furthermore, the polyurethane products produced in accordance with theinvention exhibit a reduced tendency to stain vinyl films or to degradepolycarbonate sheets with which they are exposed, display excellentadhesion properties (in appropriate formulations). These advantages areachieved by including in the reaction mixture either a polymer (b2)obtained by reaction of an epoxide (b3) with a secondary amine and/or atertiary amine molecule containing a hydrogen reactive group, or byincluding such polymers (b2) as partial carriers (feedstock or diluent)in polyols (b1) used in the preparation of SAN, PIPA or PHD copolymerpolyols and adding them to the polyol mixture (b) or by using suchpolyols in a prepolymer with a polyisocyanate alone or with anisocyanate and a second polyol.

The combination of polyols and polymers used in the present inventionwill be a combination of (b1) and (b2) as described above and eventually(b1) containing a polyol made from an amine initiation, such as, forinstance those described in WO 01/58,976 and U.S. Pat. Nos. 5,476,969and 5,672,636. As used herein the term polyols are those materialshaving at least one group containing an active hydrogen atom capable ofundergoing reaction with an isocyanate. Preferred among such compoundsare materials having at least two hydroxyls, primary or secondary, or atleast two amines, primary or secondary, carboxylic acid, or thiol groupsper molecule. Compounds having at least two hydroxyl groups or at leasttwo amine groups per molecule are especially preferred due to theirdesirable reactivity with polyisocyanates.

Suitable polyols (b1) that can be used to produce polyurethane materialswith the autocatalytic polymers (b2) of the present invention are wellknown in the art and include those described herein and any othercommercially available polyol and/or SAN, PIPA or PHD copolymer polyols.Such polyols are described in “Polyurethane Handbook”, by G. Oertel,Hanser publishers. Mixtures of one or more polyols and/or one or morecopolymer polyols may also be used to produce polyurethane productsaccording to the present invention.

Representative polyols include polyether polyols, polyester polyols,polyhydroxy-terminated acetal resins, hydroxyl-terminated amines andpolyamines. Examples of these and other suitable isocyanate-reactivematerials are described more fully in U.S. Pat. No. 4,394,491.Alternative polyols that may be used include polyalkylenecarbonate-based polyols and polyphosphate-based polyols. Preferred arepolyols prepared by adding an alkylene oxide, such as ethylene oxide(EO), propylene oxide (PO), butylene oxide (BO) or a combinationthereof, to an initiator having from 2 to 8, preferably 2 to 6 activehydrogen atoms. Catalysis for this polymerization can be either anionicor cationic, with catalysts such as KOH, CsOH, boron trifluoride, or adouble cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate orquaternary phosphazenium compound.

The polyol or blends thereof employed depends upon the end use of thepolyurethane product to be produced. The molecular weight or hydroxylnumber of the base polyol may thus be selected so as to result inflexible, semi-flexible, integral-skin or rigid foams, elastomers orcoatings, or adhesives when the polymer/polyol produced from the basepolyol is converted to a polyurethane product by reaction with anisocyanate, and depending on the end product in the presence of ablowing agent. The hydroxyl number and molecular weight of the polyol orpolyols employed can vary accordingly over a wide range. In general, thehydroxyl number of the polyols employed may range from 15 to 800.

In the production of a flexible polyurethane foam, the polyol ispreferably a polyether polyol and/or a polyester polyol. The polyolgenerally has an average functionality ranging from 2 to 5, preferably 2to 4, and an average hydroxyl number ranging from 20 to 100 mg KOH/g,preferably from 20 to 70 mgKOH/g. As a further refinement, the specificfoam application will likewise influence the choice of base polyol. Asan example, for molded foam, the hydroxyl number of the base polyol maybe on the order of 20 to 60 with ethylene oxide (EO) capping, and forslabstock foams the hydroxyl number may be on the order of 25 to 75 andis either mixed feed EO/PO (propylene oxide) or is only slightly cappedwith EO or is 100 percent PO based. For elastomer applications, it willgenerally be desirable to utilize relatively high molecular weight basepolyols, from 2,000 to 8,000, having relatively low hydroxyl numbers,for example, 20 to 50.

Typically polyols suitable for preparing rigid polyurethanes includethose having an average molecular weight of 100 to 10,000 and preferably200 to 7,000. Such polyols also advantageously have a functionality ofat least 2, preferably 3, and up to 8, preferably up to 6, activehydrogen atoms per molecule. The polyols used for rigid foams generallyhave a hydroxyl number of 200 to 1,200 and more preferably from 300 to800.

For the production of semi-rigid foams, it is preferred to use atrifunctional polyol with a hydroxyl number of 30 to 80.

The initiators for the production of polyols (b1) generally have 2 to 8functional groups that will react with the alkylene oxide. Examples ofsuitable initiator molecules are water, organic dicarboxylic acids, suchas succinic acid, adipic acid, phthalic acid and terephthalic acid andpolyhydric; in particular dihydric to octahydric alcohols or dialkyleneglycols, for example ethanediol, 1,2- and 1,3-propanediol, diethyleneglycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol,trimethylolpropane, pentaerythritol, sorbitol and sucrose or blendsthereof. Other initiators include compounds linear and cyclic aminecompounds containing eventually a tertiary amine such as ethanoldiamine,triethanoldiamine, and various isomers of toluene diamine,ethylenediamine, N-methyl-1,2-ethanediamine,N-Methyl-1,3-propanediamine, N,N-dimethyl-1,3-diaminopropane,N,N-dimethylethanolamine, 3,3′-diamino-N-methyldipropylamine,aminopropyl-imidazole.

Amine based polyol (b1) can also contain a tertiary nitrogen in thechain, by using for instance an alkyl-aziridine as co-monomer with POand EO, or (b1) can be capped with this teriary amine, by using forexample a N,N-dialkyl-glycidylamine.

The epoxides for producing the catalytic polymers (b2) are known in theart. See for example, U.S. Pat. No. 4,609,685. The epoxide materials canbe monomeric or polymeric, saturated or unsaturated, aliphatic,cycloaliphatic, aromatic or heterocyclic and may be substituted ifdesired with other substituents besides the epoxy groups, for example,hydroxyl, ether radicals and aromatic halogen atoms. Preferred epoxidesare aliphatic or cycloaliphatic polyepoxides, more preferably diepoxidesor triepoxides.

Particularly useful polyepoxide compounds which can be used in thepractice of the present invention are polyepoxides having the followinggeneral formula:

wherein R is substituted or unsubstituted aromatic, alphatic,cycloaliphatic or heterocyclic polyvalent group and n had an averagevalue of from 1 to less than 8.

Examples of common epoxy resins include for example, the diglycidylethers of resorcinol, catechol, hydroquinone, bisphenol, bisphenol A,bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenyl ethane), bisphenol F,bisphenol K, tetrabromobisphenol A, phenol-formaldehyde novolac resins,alkyl substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyderesins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenolresins, trimethylolpropane triglycidyl ether,dicyclopentadiene-substituted phenol resins tetramethylbiphenol,tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol,tetrachlorobisphenol A and any combination thereof.

Examples of preferred diepoxides are hydrogenated liquid aromatic epoxyresins of bis-phenol A or bisphenol F; and diepoxides D.E.R. 736, D.E.R.732 (aliphatic epoxides) and ERL-4221 (cyclic aliphatic epoxide)available from The Dow Chemical Company. A mixture of any two or morepolyexpoxides can be used in the practice of the present invention.Preferably the epoxide resin has an average equivalent weight of 90 to500. More preferably the epoxy resin has an average equivalent weight of150 to 400.

Polyepoxides can be prepared by epoxidizing the corresponding allylethers or reacting a molar excess of epichlorohydrin and an aromaticpolyhydroxy compound, such as novolak, isopropylidne bisphenol,resorcinol, etc. Polyepoxides can also be obtained by reacting anepihalohydrin with either a polyhydric phenol or a polyhydric alcohol.

Usually epoxide resins contain a relatively high amount of chlorine,both under the form of chloromethyl groups and as ionic chloride. Forinstance D.E.R. 736, an epoxide resin available from The Dow ChemicalCompany, has about 10 percent total chlorine. Of particular interest forthe present invention are low chlorine epoxy resins with less than 5percent and more preferably less than 1 percent total chlorine.

The amine compounds for producing the autocatalytic polyols of (b2) arethose which react with an epoxide moiety to produce a tertiary amine.Such compounds include secondary amines and/or molecules which contain atertiary amine and at least one reactive hydrogen able to react with anepoxide. Groups reactive with epoxides include primary or secondary,aliphatic or aromatic amines; primary, secondary and/or tertiaryalcohols; amides; ureas; and urethanes.

Generally, secondary amines can be represented by HNR₂ ¹ where each R¹is independently a moiety having 1 to 20 carbon atoms, such as a linearor branched alkyl or alkylaryl, or may be attached together with thenitrogen atom and optionally other hetero atoms and alkyl-substitutedhetero atoms to form one or two saturated heterocyclic or aromaticring(s).

Compounds containing at least one tertiary nitrogen and at least onehydrogen atom reactive to an epoxide can be represented by(R³)_(x)-A-(R²-M)_(x)-(R²)_(y)where A is either hydrogen, nitrogen or oxygen;

-   x is 0, 1 or 2;-   z is 1 or 2-   with the provisos x is zero when A is hydrogen, x and z are 1 when A    is oxygen, and when A is nitrogen x and z can be 1 or 2 with the sum    of x and z being 3;-   R² at each occurrence is independently a moiety having 1 to 20    carbon atoms;-   R³ is hydrogen or a moiety having 1 to 20 carbon atoms;-   M is an amine or polyamine, linear, branched or cyclic, with at    least one tertiary amine group; and-   y is an integer from 0 to 6. Preferably M has a molecular weight of    30 to 300. More preferably M has a molecular weight of 50 to 200.

Examples of amines that are commercially available and that can be usedto manufacture polyols of (b2), specifically (b2a), (b2b), (b2c), aredimethylamine, diethylamine, N,N-dimethylethanolamine,N,N-dimethyl-N′-ethylenediamine, 3-dimethylamino-1-propanol,1-dimethylamino-2-propanol, 3-(dimethylamino) propylamine,dicyclohexylamine, 1-(3-aminopropyl)-imidazole, 3-hydroxymethylquinuclidine, imidazole, 2-methyl imidazole,1-(2-aminoethyl)-piperazine, 1-methyl-piperazine, 3-quinuclidinol,tetramethylamino-bis-propylamine, 2-(2-aminoethoxy)-ethanol,N,N-dimethylaminoethyl-N′-methyl ethanolamine and2-(methylamino)-ethanol. Other types of amines which can be used withthe present invention are N,N′-dimethylethylenediamine,4,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine,2,4-diamino-6-methyl-1,3,5-triazine, 3-aminopyridine,2,4-diaminopyrimidine,2-phenyl-imino-3-(2-hydroxyethyl)-oxazalodine,N-(-2-hydroxyethyl)-2-methyl-tetrahydropyrimidine,N-(2-hydroxyethyl)-imidazoline,2,4-bis-(N-methyl-2-hydroxytethylamino)-6-phenyl-1,3,5-triazine,bis-(dimethylaminopropyl)amino-2-propanol,2-(2-methylaminoethyl)-pyridine, 2-(methylamino)-pyridine,2-methylaminomethyl-1,3-dioxane, and dimethylaminopropyl urea.

Amines used in the present invention can also be polymers, such as aminecapped polyols or polyamines. In that case monomeric epoxy compounds arepreferred.

The autocatalytic polymers (b2) are epoxides reacted with an amine basedcompound as described above. When using a polyepoxide resin it ispreferred to have at least 70 percent of these epoxide groups reactedwith the amine, more preferably 90 percent and most preferably 100percent. More than one amine or aminoalcohols can be reacted with theepoxide resin.

The production of polymers (b2) is based on the reactions of an epoxidewith at least one amine based molecule to obtain a tertiary aminefunction in the final polymer molecule. The two or more reactants can bemixed together or the epoxide can first be pre-reacted partially withthe amine(s) before further addition or vice versa the amine(s) can bein excess at the beginning of the reaction. Stoichiometric ratio betweenthe amine and the epoxy resin can be used, or excess of one of thecomponents may be favored to adjust final product characteristics.Addition of heat or cooling and proper catalysis may be used to controlthese reactions. Additionally other compounds can be used to helpproducing these amine epoxy adducts, that is co-reactants, solvents etc.It is important to note that these epoxide-reactive hydrogen reactionsgenerate hydroxyl groups.

The properties of the autocatalytic polyols (b2) can vary widely asdescribed above for polyol (b1) and such parameters as average molecularweight, hydroxyl number, functionality, etc. will generally be selectedbased on the end use application of the formulation, that is, what typeof polyurethane product.

The polymers of (b2) include conditions where the polymer is reactedwith a polyisocyanate to form a prepolymer and subsequently a polyol isoptionally added to such a prepolymer.

The limitations described with respect to the characteristics of thepolyols (b1) and polymer (b2) above are not intended to be restrictivebut are merely illustrative of the large number of possible combinationsfor the polyol or polyols used.

In a preferred embodiment the epoxide of polymer (b2) is a diepoxide andthe amine based molecule containing at least one reactive hydrogen has amethyl-amino or a dimethyl amino or an amidine or a pyridine or apyrimidine or a quinuclidine or an adamantane or a triazine or animidazole or a piperazine structure combined with secondary and/orprimary amines and/or secondary and/or primary hydroxyls.

The weight ratio of (b1) to (b2) will vary depending on the amount ofadditional catalyst one may desire to add to the reaction mix and to thereaction profile required by the specific application. Generally if areaction mixture with a base level of catalyst having specified curingtime, (b2) is added in an amount so that the curing time is equivalentwhere the reaction mix contains at least 10 percent by weight lesscatalyst. Preferably the addition of (b2) is added to give a reactionmixture containing 20 percent less catalyst than the base level. Morepreferably the addition of (b2) will reduce the amount of catalystrequired by 30 percent over the base level. For some applications, themost preferred level of (b2) addition is where the need for a fugitiveor reactive tertiary amine catalysts or organometallic salt iseliminated.

Combination of two or more autocatalytic polymers of (b2) type can alsobe used with satisfactory results in a single polyurethane formulationwhen one wants for instance to adjust blowing and gelling reactionsmodifying the epoxide and/or the amine structures with differenttertiary amines, functionalities, equivalent weights, etc, and theirrespective amounts in the formulations.

Polyols pre-reacted with polyisocyanates and polymer (b2) with no freeisocyanate functions can also be used in the polyurethane formulation.Isocyanate prepolymers based on polyol (b2) can be prepared withstandard equipment, using conventional methods, such a heating thepolyol (b2) in a reactor and adding slowly the isocyanate under stirringand then adding eventually a second polyol, or by prereacting a firstpolyol with a diisocyanate and then adding polymer (b2).

The isocyanates which may be used with the autocatalytic polymers of thepresent invention include aliphatic, cycloaliphatic, arylaliphatic andaromatic isocyanates. Aromatic isocyanates, especially aromaticpolyisocyanates are preferred.

Examples of suitable aromatic isocyanates include the 4,4′-, 2,4′ and2,2′-isomers of diphenylmethane diisocyante (MDI), blends thereof andpolymeric and monomeric MDI blends toluene-2,4- and 2,6-diisocyanates(TDI), m- and p-phenylenediisocyanate, chlorophenylene-2,4-diisocyanate,diphenylene-4,4′-diisocyanate, 4,4′-diisocyanate-3,3′-dimehtyldiphenyl,3-methyldiphenyl-methane-4,4′-diisocyanate and diphenyletherdiisocyanateand 2,4,6-triisocyanatotoluene and 2,4,4′-triisocyanatodiphenylether.

Mixtures of isocyanates may be used, such as the commercially availablemixtures of 2,4- and 2,6-isomers of toluene diisocyantes. A crudepolyisocyanate may also be used in the practice of this invention, suchas crude toluene diisocyanate obtained by the phosgenation of a mixtureof toluene diamine or the crude diphenylmethane diisocyanate obtained bythe phosgenation of crude methylene diphenylamine. TDI/MDI blends mayalso be used. MDI or TDI based prepolymers can also be used, made eitherwith polyol (b1), polyol (b2) or any other polyol as describedheretofore. Isocyanate-terminated prepolymers are prepared by reactingan excess of polyisocyanate with polyols, including aminated polyols orimines/enamines thereof, or polyamines.

Examples of aliphatic polyisocyanates include ethylene diisocyanate,1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane1,4-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, saturatedanalogues of the above mentioned aromatic isocyanates and mixturesthereof.

The preferred polyisocyantes for the production of rigid or semi-rigidfoams are polymethylene polyphenylene isocyanates, the 2,2′, 2,4′ and4,4′ isomers of diphenylmethylene diisocyanate and mixtures thereof. Forthe production of flexible foams, the preferred polyisocyanates are thetoluene-2,4- and 2,6-diisocyanates or MDI or combinations of TDI/MDI orprepolymers made therefrom.

Isocyanate tipped prepolymer based on polymer (b2) can also be used inthe polyurethane formulation.

For rigid foam, the organic polyisocyanates and the isocyanate reactivecompounds are reacted in such amounts that the isocyanate index, definedas the number or equivalents of NCO groups divided by the total numberof isocyanate reactive hydrogen atom equivalents multiplied by 100,ranges from 80 to less than 500 preferably from 90 to 100 in the case ofpolyurethane foams, and from 100 to 300 in the case of combinationpolyurethane-polyisocyanurate foams. For flexible foams, this isocyanateindex is generally between 50 and 120 and preferably between 75 and 110.

For elastomers, coating and adhesives the isocyanate index is generallybetween 80 and 125, preferably between 100 to 110.

For producing a polyurethane-based foam, a blowing agent is generallyrequired. In the production of flexible polyurethane foams, water ispreferred as a blowing agent. The amount of water is preferably in therange of from 0.5 to 10 parts by weight, more preferably from 2 to 7parts by weight based on 100 parts by weight of the polyol. Carboxylicacids or salts are also used as reactive blowing agents. Other blowingagents can be liquid or gaseous carbon dioxide, methylene chloride,acetone, pentane, isopentane, methylal or dimethoxymethane,dimethylcarbonate. Use of artificially reduced atmospheric pressure canalso be contemplated with the present invention.

In the production of rigid polyurethane foams, the blowing agentincludes water, and mixtures of water with a hydrocarbon, or a fully orpartially halogenated aliphatic hydrocarbon. The amount of water ispreferably in the range of from 2 to 15 parts by weight, more preferablyfrom 2 to 10 parts by weight based on 100 parts of the polyol. Withexcessive amount of water, the curing rate becomes lower, the blowingprocess range becomes narrower, the foam density becomes lower, or themoldability becomes worse. The amount of hydrocarbon, thehydrochlorofluorocarbon, or the hydrofluorocarbon to be combined withthe water is suitably selected depending on the desired density of thefoam, and is preferably not more than 40 parts by weight, morepreferably not more than 30 parts by weight based on 100 parts by weightof the polyol. When water is present as an additional blowing agent, itis generally present in an amount from 0.5 to 10, preferably from 0.8 to6 and more preferably from 1 to 4 and most preferably from 1 to 3 partsby total weight of the total polyol composition.

Hydrocarbon blowing agents are volatile C₁ to C₅ hydrocarbons. The useof hydrocarbons is known in the art as disclosed in EP 421 269 and EP695 322. Preferred hydrocarbon blowing agents are butane and isomersthereof, pentane and isomers thereof (including cyclopentane), andcombinations thereof.

Examples of fluorocarbons include methyl fluoride, perfluoromethane,ethyl fluoride, 1,1-difluoroethane, 1,1,1-trifluoroethane (HFC-143a),1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane,difluoromethane, perfluoroethane, 2,2-difluoropropane,1,1,1-trifluoropropane, perfluoropropane, dichloropropane,difluoropropane, perfluorobutane, perfluorocyclobutane.

Partially halogenated chlorocarbons and chlorofluorocarbons for use inthis invention include methyl chloride, methylene chloride, ethylchloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane(FCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b),1,1-dichloro-2,2,2-trifluoroethane (HCHC-123) and1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124).

Fully halogenated chlorofluorocarbons include trichloromonofluoromethane(CFC-11) dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane(CFC-113), 1,1,1-trifluoroethane, pentafluoroethane,dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, anddichlorohexafluoropropane. The halocarbon blowing agents may be used inconjunction with low-boiling hydrocarbons such as butane, pentane(including the isomers thereof), hexane, or cyclohexane or with water.

In addition to the foregoing critical components, it is often desirableto employ certain other ingredients in preparing polyurethane polymers.Among these additional ingredients are surfactants, preservatives, flameretardants, colorants, antioxidants, reinforcing agents, stabilizers andfillers.

In making polyurethane foam, it is generally preferred to employ anamount of a surfactant to stabilize the foaming reaction mixture untilit cures. Such surfactants advantageously comprise a liquid or solidorganosilicone surfactant. Other surfactants include polyethylene glycolethers of long-chain alcohols, tertiary amine or alkanolamine salts oflong-chain alkyl acid sulfate esters, alkyl sulfonic esters and alkylarylsulfonic acids. Such surfactants are employed in amounts sufficientto stabilize the foaming reaction mixture against collapse and theformation of large, uneven cells. Typically, 0.2 to 3 parts of thesurfactant per 100 parts by weight total polyol (b) are sufficient forthis purpose.

One or more catalysts for the reaction of the polyol (and water, ifpresent) with the polyisocyanate can be used. Any suitable urethanecatalyst may be used, including tertiary amine compounds, amines withisocyanate reactive groups and organometallic compounds. Preferably thereaction is carried out in the absence of an amine or an organometalliccatalyst or a reduced amount as described above. Exemplary tertiaryamine compounds include triethylenediamine, N-methylmorpholine,N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine,tetramethylethylenediamine, bis (dimethylaminoethyl)ether,1-methyl-4-dimethylaminoethyl-piperazine,3-methoxy-N-dimethylpropylamine, N-ethylmorpholine,dimethylethanolamine, N-cocomorpholine, N,N-dimethyl-N′,N′-dimethylisopropylpropylenediamine, N,N-diethyl-3-diethylamino-propylamine anddimethylbenzylamine. Exemplary organometallic catalysts includeorganomercury, organolead, organoferric and organotin catalysts, withorganotin catalysts being preferred among these. Suitable tin catalystsinclude stannous chloride, tin salts of carboxylic acids such asdibutyltin di-laurate, as well as other organometallic compounds such asare disclosed in U.S. Pat. No. 2,846,408, or in EP 1,013,704, EP1,167,410, EP 1,167,411. A catalyst for the trimerization ofpolyisocyanates, resulting in a polyisocyanurate, such as an alkalimetal alkoxide may also optionally be employed herein. The amount ofamine catalysts can vary from 0.02 to 5 percent in the formulation ororganometallic catalysts from 0.001 to 1 percent in the formulation canbe used.

A crosslinking agent or a chain extender may be added, if necessary. Thecrosslinking agent or the chain extender includes low-molecularpolyhydric alcohols such as ethylene glycol, diethylene glycol,1,4-butanediol, and glycerin; low-molecular amine polyol such asdiethanolamine and triethanolamine; polyamines such as ethylene diamine,xlylenediamine, and methylene-bis(o-chloroaniline). The use of suchcrosslinking agents or chain extenders is known in the art as disclosedin U.S. Pat. Nos. 4,863,979 and 4,963,399 and EP 549,120.

When preparing rigid foams for use in construction, a flame retardant isgenerally included as an additive. Any known liquid or solid flameretardant can be used with the autocatalytic polyols of the presentinvention. Generally such flame retardant agents are halogen-substitutedphosphates and inorganic flame proofing agents. Commonhalogen-substituted phosphates are tricresyl phosphate,tris(1,3-dichloropropyl phosphate, tris(2,3-dibromopropyl) phosphate andtetrakis (2-chloroethyl)ethylene diphosphate. Inorganic flame retardantsinclude red phosphorous, aluminum oxide hydrate, antimony trioxide,ammonium sulfate, expandable graphite, urea or melamine cyanurate ormixtures of at least two flame retardants. In general, when present,flame retardants are added at a level of from 5 to 50 parts by weight,preferable from 5 to 25 parts by weight of the flame retardant per 100parts per weight of the total polyol present.

The applications for foams produced by the present invention are thoseknown in the industry. For example rigid foams are used in theconstruction industry and for insulation for appliances andrefrigerators. Flexible foams and elastomers find use in applicationssuch as furniture, shoe soles, automobile seats, sun visors, steeringwheels, armrests, door panels, noise insulation parts and dashboards.

Processing for producing polyurethane products are well known in theart. In general components of the polyurethane-forming reaction mixturemay be mixed together in any convenient manner, for example by using anyof the mixing equipment described in the prior art for the purpose suchas described in “polyurethane Handbook”, by G. Oertel, Hanser publisher.

The polyurethane products are either produced continuously ordiscontinuously, by injection, pouring, spraying, casting, calendering,etc; these are made under free rise or molded conditions, with orwithout release agents, in-mold coating, or any inserts or skin put inthe mold. In case of flexible foams, those can be mono- ordual-hardness.

For producing rigid foams, the known one-shot prepolymer orsemi-prepolymer techniques may be used together with conventional mixingmethods including impingement mixing. The rigid foam may also beproduced in the form of slabstock, moldings, cavity filling, sprayedfoam, frothed foam or laminates with other material such as paper,metal, plastics or wood-board. Flexible foams are either free rise andmolded while microcellular elastomers are usually molded.

The following examples are given to illustrate the invention and shouldnot be interpreted as limiting in anyway. Unless stated otherwise, allparts and percentages are given by weight.

A description of the raw materials used in the examples is as follows.DEOA 85 percent is 85 percent pure diethanolamine and 15 percent water.DMAPA is 3-dimethylamino-1-propylamine. 2-Methylimidazole is a tertiaryamine with a reactive hydrogen available from Aldrich. ETA isEthanolamine available from Aldrich D.E. R. 732 is an aliphaticdiepoxide resin with an EEW (epoxy equivalent weight) of 325 availablefrom The Dow Chemical Company Epoxide resin A is an aliphatic diepoxideresin with an EEW (epoxy equivalent weight) of 325 and containing lessthan 1 percent Chloride. Dabco DC 5169 is a silicone-based surfactantavailable from Air Products and Chemicals Inc. Dabco 33 LV is a tertiaryamine catalyst available from Air Products and Chemicals Inc. Niax A-1is a tertiary amine catalyst available from Crompton Corporation. PolyolB is a 1,700 equivalent weight propoxylated tetrol initiated with3,3′-diamino-N-methyl dipropylamine and capped with 15 percent Ethyleneoxide. SPECFLEX NC 632 is a 1,700 EW polyoxypropylene polyoxyethylenepolyol initiated with a blend of glycerol and sorbitol available fromThe Dow Chemical Company. SPECFLEX NC-700 is a 40 percent SAN basedcopolymer polyol with an average hydroxyl number of 20 available fromThe Dow Chemical Company. VORANATE T-80 is TDI 80/20 isocyanateavailable from The Dow Chemical Company.

All foams were made in the laboratory with an Admiral high pressuremachine equipped with Krauss-Maffei MK-12/16-UL-4K mix-head and bypreblending polyols, surfactants, crosslinkers, catalysts and water. Thereactants are poured in a 40×40×10 cm aluminum mold heated at 60° C.which is subsequently closed. The mold had previously been sprayed withthe release agent Klueber 41-2013 available from Klueber Chemie. Curingat 4 minutes is assessed by manually demolding the part, looking fordefects and measuring the 50 percent Indentation force first cycle(crushing Force) and same measurement after foam crushing (Hot IFD).Free rise reactivity with cream, gel and rise times, as defined in“Flexible Polyurethane Foams” by Ron Herrington et al, ed The DowChemical Company, are also recorded.

BVT (Brookfield Viscosity) tests are carried out as follows: 100 gramsof Specflex NC-632 are allowed to equilibrate at 25° C. and then blendedwith the autocatalytic polymer. Voranate T-80 is then added at aconcentration corresponding to an index of 110. The viscosity build upover time is measured until full gelation (20,000 mPa·s) is reached.This time is recorded as well as final viscosity if gelation is notobtained after 11 minutes. In the case of autocatalytic polymers, theseare blended at various ratios with the control polyol. In all cases nocatalysts are added.

EXAMPLE 1

A one liter flask was charged with 100 grams (1.218 mole) of2-methylimidazole and 264.5 grams (0.814 mole epoxide groups) of D.E.R.732. The flask was fitted with an addition funnel containing anadditional 250 grams (0.770 mole epoxy groups) of D.E.R. 732 and placedunder an atmosphere of nitrogen. The flask was placed in a heating bathat 60° C. The internal temperature was controlled at 60° C. by applyingheating or cooling as necessary. After 3 hours of reaction time, thecontents of the addition funnel were added dropwise over the course of 4hours. The highest observed temperature during the reaction was 78° C.After all the D.E.R. had been added, the reaction mixture was stirred at60° C. overnight. A light yellow syrup, 603.7 grams was obtained. Theproduct contains 1.988 mmol/g of 2-methylimidazole derived species. Thelevel of ionic chloride in the sample is 43,000 ppm.

EXAMPLE 2

A 100 mL flask was charged with 12.5 grams (152.2 mmole) of2-methylimidazole, and 28.2 grams (99 mmole epoxide groups) of epoxideresin A. The flask was fitted with an addition funnel containing anadditional 28.2 grams of epoxide resin A and placed under an atmosphereof nitrogen. The flask was placed in a heating bath at 60° C. Theinternal temperature was controlled at 60° C. by applying heating orcooling as necessary. After 2 hours of reaction time, the contents ofthe addition funnel were added dropwise over the course of 6 hours. Thehighest observed temperature during the reaction was 65° C. After allthe D.E.R. had been added, the reaction mixture was stirred at 60° C.overnight. A red/brown syrup, 66.9 grams, was obtained. The level ofionic chloride in the sample is less than 1 ppm.

EXAMPLES 3 and 4

The procedure of Example 2 was followed using the following components,parts by weight:

-   -   (3) Epoxide A/ETA/2-Methylimidazole 83.95/3.7/12.35    -   (4) Epoxide A/DMAPA/2-Methylimidazole 84.4/5.3 /10.3

The final product in both cases was a liquid syrup.

EXAMPLES 5, 6, 7, 8

BVT tests were carried out with these samples and compared with straight2-methylimidazole and with Dabco 33LV (triethylenediamine), aconventional amine catalyst. Both amines were dissolved in 5 parts byweight of NMP (1-methyl-2-pyrrolidinone) prior to addition of 95 partsby weight of Specflex NC-632. Results are reported in the table below:Example Comparative Comparative 5 6 7 8 A B Type of catalyst ExampleExample Example Example Dabco 2-Methyl- 1 2 3 4 33 LV imidazole Level ofproduct 3 0.5 0.6 0.6 0.26 0.5 (percent) Time to gel (s) 390 450 135 245400 NA Viscosity at 11 min >20,000 >20,000 >20,000 >20,000 >20,000 2,100(mPa · s)

These examples 5 to 8 show that these amine-epoxide adducts are verypotent autocatalytic polymers, especially the polymer of examples 2 and6 based on low chlorine epoxy resin A. The results also show that2-methylimidazole is not a strong catalyst by itself since it did notgive full gelation after 11 minutes.

EXAMPLES 9, 10, 11, 12 and 13

Good foam pads were produced with the following formulation: Amine-epoxyadduct x Specflex NC-632 (20 − x) Specflex NC-700 30 Polyol B 50 Water3.5 DEOA 85 percent 0.8 Dabco DC-5169 0.6 Voranate T-80 index 100

In formulation of example 13 Polyol B is replaced by Specflex NC-632 and0.05 PHP Niax A-1 is added instead. Comparative example C has noamine-epoxy adduct and no amine catalyst. Comparative example D contains0.4 PHP Dabco 33 LV Results are reported in table below: ExampleComparative Comparative 9 10 11 12 C D 13 Adduct of example 1 2 3 4 Noamine Dabco 33 LV 2 catalyst 0.4 PHP Level x (PHP) 2.0 1.5 2.7 2.7 0 01.5 Cream time (s) 3 5 3 4 NA 4 3 Gel time (s) 50 53 40 44 NA 53 53 Risetime (s) 100 103 65 72 NA 96 89 Part weight (g) 590 604 612 609 Partial600 600 collapse Crushing Force (N) 730 1,080 1,360 1,030 Uncured 1,2401,100 Hot IFD (N) 120 150 180 155 NA 180 140

EXAMPLE 14

The foam of example 9 was tested for volatiles according to AUDI-PV 3341and for VOC (Volatile Organic Components) and FOG (Fogging) according toDaimler-Chrysler PB-VWT-709 test methods. No amine volatiles-weredetected from these foams.

Other embodiments of the invention will be apparent to those skilled inthe art from a consideration of this specification or practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with the true scope and spiritof the invention being indicated by the following claims.

1. A process for the production of a polyurethane product by reaction ofa mixture of (a) at least one organic polyisocyanate with (b) a polyolcomposition comprising (b1) from 60 to 99.5 percent by weight of apolyol compound having a functionality of 2 to 8 and a hydroxyl numberof from 15 to 800 and (b2) from 0.5 to 40 percent by weight of at leastone polymer compound having a functionality of 1 to 12, a hydroxylnumber of from 20 to 600 and containing at least one tertiary aminegroup, wherein the weight percent is based on the total amount of polyolcomposition (b), and (b2) is obtained by the reactions of an epoxy resin(b3) and an amine wherein the amine is either a primary or a secondaryamine or a molecule containing at least one tertiary nitrogen and atleast one reactive hydrogen able to react with the epoxide; or (b2) is(b4) a hydroxyl-tipped prepolymer obtained from the reaction of anexcess of (b2) or a mixture thereof with a polyisocyanate; or (b2) is(b5) a blend of several epoxides (b3) modified with one or more types ofamines containing each at least one reactive hydrogen; (c) optionally inthe presence of a blowing agent; and (d) optionally additives orauxiliary agents known per se for the production of polyurethane foams,elastomers and/or coatings.
 2. The process of claim 1 wherein polyol(b1) comprises a polyether polyol, polyester polyol,polyhydroxy-terminated acetal resin, hydroxyl-terminated amine polyol,hydroxyl-terminated polyamine polyol or a mixture thereof.
 3. Theprocess of claim 1 wherein polyol (b1) comprises a polyester polyol, apolyether polyol or a mixture thereof.
 4. The process of claim 1 whereinthe secondary amine used for obtaining a polyol of (b2) is representedby HNR¹ ₂ where each R¹ is independently a compound having 1 to 20carbon atoms or may be attached together with the nitrogen atom andoptionally other hetero atoms and alkyl-substituted hetero atoms to formone or two saturated heterocyclic or aromatic ring(s).
 5. The process ofclaim 1 wherein the tertiary amine used for obtaining a polyol of (b2),is represented by(R³)_(x)-A-(R²-M)_(z)—(R²)_(y) where A is either hydrogen, nitrogen oroxygen; x is 0, 1 or 2; z is 1 or 2 with the provisos x is zero when Ais hydrogen, x and z are 1 when A is oxygen, and when A is nitrogen xand z can be 1 or 2 with the sum of x and z being 3; R² at eachoccurrence is independently a moiety having 1 to 20 carbon atoms; R³ ishydrogen or a moiety having 1 to 20 carbon atoms; M is an amine orpolyamine, linear, branched or cyclic, with at least one tertiary aminegroup; and y is an integer from 0 to
 6. 6. The process of claim 1wherein the secondary or tertiary amine used for the production ofpolyol (b2) is one or more amines selected from the group consisting ofdimethylamine, diethylamine, N,N-dimethylethanolamine,N,N-dimethyl-N′-ethylenediamine, 3-dimethylamino-1-propanol,1-dimethylamino-2-propanol, 3-(dimethylamino) propylamine,dicyclohexylamine, 1-(3-aminopropyl)-imidazole, 3-hydroxymethylquinuclidine, imidazole, 2-methyl imidazole,1-(2-aminoethyl)-piperazine, 1-methyl-piperazine, 3-quinuclidinol,tetramethylamino-bis-propylamine, 2-(2-aminoethoxy)-ethanol,N,N-dimethylaminoethyl-N′-methyl ethanolamine and2-(methylamino)-ethanol.
 7. The process of claim 1 wherein the secondaryor tertiary amine used for the production of polyol (b2) is one or moreamines selected from the group consisting ofN,N′-dimethylethylenediamine, 4,6-dihydroxypyrimidine,2,4-diamino-6-hydroxypyrimidine, 2,4-diamino-6-methyl-1,3,5-triazine,3-aminopyridine, 2,4-diaminopyrimidine,2-phenyl-imino-3-(2-hydroxyethyl)-oxazalodine,N-(−2-hydroxyethyl)-2-methyl-tetrahydropyrimidine,N-(2-hydroxyethyl)-imidazoline,2,4-bis-(N-methyl-2-hydroxytethylamino)-6-phenyl-1,3,5-triazine,bis-(dimethylaminopropyl)amino-2-propanol,2-(2-methylaminoethyl)-pyridine, 2-(methylamino)-pyridine,2-methylaminomethyl-1,3-dioxane and dimethylaminopropyl urea.
 8. Theprocess of claim 1 wherein the epoxy resin for the production of polyol(b2) is represented by the general formula general formula:

wherein R is substituted or unsubstituted aromatic, alphatic,cycloaliphatic or heterocyclic polyvalent group and n had an averagevalue of from 1 to less than
 8. 9. The process of claim 1 wherein theepoxy resin for the production of polyol (b2) is selected from one ormore of the group consisting-diglycidyl ethers of resorcinol, catechol,hydroquinone, bisphenol, bisphenol A, bisphenol AP(1,1-bis(4-hydroxylphenyl)-1-phenyl ethane), bisphenol F, bisphenol K,tetrabromobisphenol A, phenol-formaldehyde novolac resins, alkylsubstituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyderesins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenolresins, trimethylolpropane triglycidyl ether,dicyclopentadiene-substituted phenol resins tetramethylbiphenol,tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol, andtetrachlorobisphenol A and aliphatic diepxoids.
 10. The process of claim9 wherein the epoxy resin for the production of polyol (b2) is analiphatic diepoxide.
 11. The process of any one of claims 1-10 whereinthe polyurethane product is a rigid foam and the polyol (b1) and (b2)have an average functionality of 3 to 6 and an average hydroxyl numberof 200 to
 800. 12. The process of claim 11 wherein the blowing agent forproducing the rigid foam is a hydrocarbon, a hydrochlorofluorocarbon, ahydrofluorocarbon, a hydrochlorocarbon or a mixture thereof.
 13. A rigidfoam produced by the process of claim
 12. 14. The process of any one ofclaim 1-10 wherein the polyurethane product is a flexible foam and thepolyol (b1) and (b2) have an average functionality of 2 to 4 and anaverage hydroxyl number of 20 to
 100. 15. A flexible foam produced bythe process of claim
 14. 16. A polyol formulation comprising (b1) from60 to 99.5 percent by weight of a polyol compound having a functionalityof 2 to 8 and a hydroxyl number of from 15 to 800 and (b2) from 0.5 to40 percent by weight of at least one polymer compound having afunctionality of 2 to 12, a hydroxyl number of from 20 to 600 andcontaining at least one tertiary amine group, wherein the weight percentis based on the total amount of polyol composition (b), and (b2) isobtained by the reactions of an epoxy resin (b3) and an amine whereinthe amine is either a primary or a secondary amine or a moleculecontaining at least one tertiary nitrogen and at least one reactivehydrogen able to react with the peroxide; or (b2) is (b4) ahydroxyl-tipped prepolymer obtained from the reaction of an excess of(b2) or a mixture thereof with a polyisocyanate; or (b2) is (b5) a blendof several epoxides (b3) modified with one or more types of aminescontaining each at least one reactive hydrogen.